EP0352875B1 - Composition de résine de polystyrène à rigidité modifiée - Google Patents

Composition de résine de polystyrène à rigidité modifiée Download PDF

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Publication number
EP0352875B1
EP0352875B1 EP89300102A EP89300102A EP0352875B1 EP 0352875 B1 EP0352875 B1 EP 0352875B1 EP 89300102 A EP89300102 A EP 89300102A EP 89300102 A EP89300102 A EP 89300102A EP 0352875 B1 EP0352875 B1 EP 0352875B1
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EP
European Patent Office
Prior art keywords
weight
polystyrene resin
parts
resin composition
potassium titanate
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EP89300102A
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German (de)
English (en)
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EP0352875A2 (fr
EP0352875A3 (en
Inventor
Masashi Sakamoto
Akifumi Tohara
Kiyoshi Koutou
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Chemical Industry Co Ltd
Asahi Kasei Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers

Definitions

  • the present invention relates to a polystyrene resin composition having improved stiffness. More particularly, the present invention is concerned with a polystyrene resin composition comprising a rubber-reinforced polystyrene resin, a fibrous potassium titanate and a higher fatty acid and/or its metal salt in specific proportions, which composition has not only excellent appearance and impact strength but also extremely improved stiffness.
  • the polystyrene resin composition may include a specific amount of a flame retardant in combination with a specific amount of a carbon fiber so that the polystyrene resin composition is remarkably improved in flame retardance without sacrificing the appearance, stiffness, impact strength and melt flowability of the composition.
  • the polystyrene resin composition can be advantageously used as a material for manufacturing parts and housings of appliances, cabinets of large televisions, and the like.
  • Polystyrene resins are used in a wide variety of fields. For example, they are used as materials for preparing parts and housings of appliances, and various vessels and articles for daily life, because the polystyrene resins have both good physical properties and good moldability.
  • polystyrene resins are used as materials for large parts or large articles, e.g., cabinets for large televisions and frames for air conditioners, there are problems arising from insufficient stiffness of the polystyrene resins.
  • a fibrous potassium titanate into a polystyrene resin such as a rubber-reinforced polystyrene resin, which is a typical example of a high impact polystyrene (HIPS), and a rubber-reinforced styrene-acrylonitrile copolymer, e.g., an acrylonitrile-butadiene-styrene (ABS) resin
  • HIPS high impact polystyrene
  • ABS acrylonitrile-butadiene-styrene
  • the polystyrene resins have not only excellent stiffness and impact strength but also improved flame retardance.
  • various attempts have been made in the art. For example, it was attempted to impart high flame retardance to a polystyrene resin by incorporation of a flame retardant, such as an organohalogen compound and, at the same time, impart non-dripping properties to the resin by incorporation of an inorganic filler, such as asbestos (see, for example Japanese Patent Application Publication Specification No. 58-37333).
  • the inorganic filler when the inorganic filler is incorporated into a polystyrene resin in an amount of more than 10 parts by weight per 100 parts by weight of the polystyrene resin, the flame retardance of the resultant polystyrene resin composition become unfavorably low, that is, the resultant polystyrene resin composition shows a long glowing (combustion with no flaming) duration when subjected to a flammability test in accordance with the test for flammability of plastic materials UL-94 (published by UNDERWRITERS LABORATORIES INC., U.S.A.).
  • the amount of an inorganic filler must be limited to a low level to ensure desirable flame retardance.
  • the stiffness improvement by incorporation of the inorganic filler is not sufficient. Therefore, the above attempt does not give a solution to the goal of providing a polystyrene resin composition having both excellent flame retardance and excellent stiffness.
  • the present inventors have made extensive and intensive investigations with a view toward developing a polystyrene resin composition which is greatly improved in stiffness without sacrificing the appearance and impact strength inherent in a rubber-reinforced resin.
  • a desired polystyrene resin composition can be obtained by incorporating a fibrous potassium titanate together with a higher fatty acid or its metal salt in specific amounts into a rubber-reinforced polystyrene resin.
  • a polystyrene resin composition having improved stiffness comprising:
  • HIPS high impact polystyrene
  • U.S. Patent Nos. 4,185,049; 3,346,520; 2,862,906; 3,243,481 and 3,903,202 can be referred to.
  • a 3 to 15 % by weight solution of a rubber material in an aromatic monovinyl monomer is subjected to bulk polymerization or suspension polymerization.
  • the high impact polystyrenes used in the present invention generally have a weight average molecular weight of 150,000 to 400,000 as measured by gel permeation chromatography based on a calibration curve prepared using a standard polystyrene sample.
  • rubber materials include polybutadiene and a styrene-butadiene copolymer.
  • the rubber material in general, is present in an amount of 2 to 30 % by weight, preferably 5 to 15 % by weight, based on the weight of the rubber-reinforced polymer, and is dispersed in the matrix of the polymer as particles having an average particle diameter of 0.5 to 5 ⁇ m.
  • aromatic monovinyl monomers include styrene, ⁇ -methylstyrene and p -methylstyrene. Of these, styrene is preferably employed.
  • the above-mentioned aromatic monovinyl monomers may be employed individually or in combination.
  • Other monomers which are copolymerizable with the aromatic monovinyl monomers, such as acrylonitrile, methyl methacrylate, acrylic acid and maleic anhydride, may also be employed.
  • the amounts thereof are generally in the range of from 1 to 15 % by weight, based on the total weight of the aromatic monovinyl monomer and the monomer copolymerizable therewith. When the amount exceeds 15 % by weight, some properties of the polystyrene resin composition are adversely affected.
  • ABS resin rubber -reinforced styrene-acrylonitrile copolymer
  • ABS resin acrylonitrile-acrylonitrile copolymer
  • the resultant polystyrene resin composition has poor Izod impact strength.
  • the rubber-reinforced polymer may be used in combination with other thermoplastic resins, such as a styrenebutadiene block copolymer.
  • other thermoplastic resins such as a styrenebutadiene block copolymer.
  • the amounts thereof can be 1 to 30 % by weight, based on the total weight of the rubber-reinforced polymer and the thermoplastic resin.
  • potassium titanate whiskers having the formula: K2O ⁇ nTiO2 wherein n is an integer of 2, 4, 6 or 8.
  • K2O ⁇ 6TiO2 potassium hexatitanate
  • the fibrous potassium titanate can be prepared by various methods, such as a calcination method as described in Japanese Patent Application Publication Specification No. 42-27254; and a hydrothermal method, a flux method and a melt method which are described in a catalogue entitled "TISMO" published by Otsuka Chemical Co., Ltd., Japan, on October 1, 1986. Of these methods, a flux method is preferred from the viewpoints of production cost, production yield, and capability of producing whiskers having a relatively large fiber length.
  • the fibrous potassium titanate may be one which has been surface-treated with an amino type silane coupling agent or an epoxy type silane coupling agent.
  • Examples of such surface-treated fibrous potassium titanate include those which are available under the trade names of TISMO-D101 and TISMO-D102 (products of Otsuka Chemical Co., Ltd., Japan).
  • the fibrous potassium titanate used in the present invention generally has an average fiber length of from 10 to 60 ⁇ m and an average fiber diameter of from 0.1 to 1.5 ⁇ m.
  • the polystyrene resin composition of the present invention may include a flame retardant.
  • a flame retardant it is preferred to employ a fibrous potassium titanate having an average fiber length of 10 to 30 ⁇ m and an average fiber diameter of 0.1 to 0.8 ⁇ m, while in the case where a flame retardant is employed, it is preferred to employ a fibrous potassium titanate having an average fiber length of 20 to 60 ⁇ m and an average fiber diameter of 0.5 to 1.5 ⁇ m.
  • the fibrous potassium titanate having larger fiber length and diameter has been found to contribute mainly to prevention of glowing upon firing.
  • the fibrous potassium titanate having smaller fiber length and diameter meter is believed to contribute mainly to improvement in stiffness and appearance of the resin composition.
  • the fibrous potassium titanate is used in an amount of 2 to 50 parts by weight, preferably 10 to 50 parts by weight, more preferably 15 to 50 parts by weight, per 100 parts by weight of the rubber-reinforced polystyrene resin. If the amount of the fibrous potassium titanate is less than 2 parts by weight, no significant improvement in stiffness is exhibited, while if the amount exceeds 50 parts by weight, not only is the impact strength lowered, but also the smoothness of the surface of an ultimate shaped article is impaired.
  • a fatty acid having 12 to 22 carbon atoms or a metal salt thereof is also used in the composition of this invention.
  • a fatty acid a saturated fatty acid is preferably used.
  • Representative examples of fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid.
  • Representative examples of metals forming the metal salt of the fatty acid include metals of Groups II and III of the periodic table, such as zinc, magnesium, calcium and aluminum.
  • metal salts of fatty acids include zinc stearate, magnesium stearate, calcium stearate, zinc palmitate, magnesium palmitate, calcium palmitate, zinc behenate, magnesium behenate, calcium behenate, zinc laurate, zinc myristate and zinc arachidate.
  • these acids and metal salts stearic acid, zinc stearate, magnesium stearate and calcium stearate are preferred.
  • the above-mentioned fatty acids and metal salts thereof can be used individually or in combination.
  • 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, of a the fatty acid or a metal salt of the fatty acid are used per 100 parts by weight of the rubber-reinforced polymer.
  • the amount of fatty acid or metal salt thereof is less than 0.1 part by weight, the resultant composition has poor impact strength.
  • the amount of fatty acid or metal salt thereof exceeds 5 parts by weight, the resultant composition not only has poor heat resistance but also undergoes unfavorable discoloration.
  • the fatty acid or a metal salt of a fatty acid in the polystyrene resin composition.
  • other lubricants such as ethylenebisstearamide and the like, are used in place of the fatty acid or metal salt thereof, the resultant composition has poor impact strength so that the objective of the present invention cannot be attained.
  • incorporation of a flame retardant in combination with a carbon fiber into the polystyrene resin composition of the present invention is very effective for imparting excellent flame retardance to the polystyrene resin composition while maintaining the excellent stiffness and impact resistance of the composition. Without the incorporation of a carbon fiber, the effects aimed at cannot be satisfactorily obtained.
  • a fibrous potassium titanate having an average fiber length of 20 to 60 ⁇ m and an average fiber diameter of 0.5 to 1.5 ⁇ m.
  • the flame retardant may be an organic halogen- or phosphorus-containing flame retardant or a metal hydroxide flame retardant which is generally used for the flame retardation of a polystyrene resin.
  • organic halogen -containing flame retardants include an aromatic halogen compound, a halogenated epoxy resin, a halogenated polycarbonate resin, a halogenated aromatic vinyl polymer, a halogenated cyanurate resin, a halogenated polyphenylene ether and a halogenated polyphenylene thioether.
  • aromatic halogen compound is most preferred from the viewpoint of thermal stability.
  • organic halogen-containing flame retardants are decabromodiphenylene oxide, a brominated bisphenol epoxy resin, a brominated bisphenol phenoxy resin, a brominated bisphenol polycarbonate resin, a brominated polystyrene resin, a brominated cross-linked polystyrene resin, a brominated bisphenol cyanurate resin, a brominated polyphenylene oxide, polybromophenylene oxide and a decabromodiphenylene oxide bisphenol condensate (tetrabromobisphenol A monomer, its oligomer or the like).
  • organic phosphorus-containing flame retardants are phosphates containing no halogen atom, such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate and octyldiphenyl phosphate; phosphates containing a halogen atom, such as tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(chloropropyl) phosphate, bis(2,3 -dibromopropyl)2,3-dichloropropyl phosphate, tris(2,3-dibromopropyl) phosphate and bis(chloropropyl)monooctyl phosphate; and phosphites, such as trip
  • metal hydroxide flame retardants include aluminum hydroxide and magnesium hydroxide.
  • the organic halogen- or phosphorus-containing flame retardant or a metal hydroxide flame retardant is generally used in an amount of from 4 to 35 parts by weight, preferably from 10 to 25 parts by weight, per 100 parts by weight of the rubber-reinforced polymer.
  • a flame retardant auxiliary may be incorporated in the polystyrene resin composition in order to further promote the flame retarding effect.
  • flame retardant auxiliaries include molybdenum compounds, such as molybdenum trioxide and ammonium molybdate, and antimony compounds, such as antimony trioxide. Of these auxiliaries, antimony trioxide is most preferred.
  • the flame retardant auxiliary is generally used in an amount of from 2 to 10 parts by weight, per 100 parts by weight of the rubber-reinforced polymer.
  • Representative examples of carbon fibers are ones produced from polyacrylonitrile or a pitch.
  • the diameter of the carbon fibers is generally in the range of from 5 to 20 ⁇ m. From the viewpoint of facilitating compounding into the composition, it is preferred to use a chip-like aggregate of several thousand to several tens thousand carbon fibers having a length of 6 mm or less.
  • the carbon fiber is generally used in an amount of from 1 to 5 parts by weight, per 100 parts by weight of the rubber-reinforced polymer. When the amount of the carbon fiber is less than 1 part by weight, the glowing time of the resultant composition is unfavorably prolonged. On the other hand, when the amount of carbon fiber is greater than 5 parts by weight, the resultant polystyrene resin composition has poor appearance, moldability and impact strength.
  • the flame-retardant polystyrene resin composition of the present invention is not only excellent in flame retardance, but also excellent in stiffness as well as appearance, impact strength and melt flowability. Such excellent properties are attained by a synergistic effect attributed to the use of a fibrous potassium titanate in combination with a flame retardant and a carbon fiber.
  • the flame retardant contributes mainly to suppression of flaming and the carbon fiber contributes mainly to suppression of glowing so that a combination of a flame retardant and a carbon fiber is extremely effective with respect to flame retardation.
  • the polystyrene resin composition of the present invention may further contain customary additives, such as a plasticizer, a lubricant, an antistatic agent, an ultraviolet light absorber, an antioxidant, an inorganic filler and a colorant, in such an amount as will not lower the above-mentioned excellent properties of the polystyrene resin composition of the present invention.
  • customary additives such as a plasticizer, a lubricant, an antistatic agent, an ultraviolet light absorber, an antioxidant, an inorganic filler and a colorant, in such an amount as will not lower the above-mentioned excellent properties of the polystyrene resin composition of the present invention.
  • the polystyrene resin composition of the present invention may usually be produced by melting and blending the above-mentioned components by means of a customary apparatus, such as an extruder, a kneader, a Banbury mixer and a roll mill, extruding the resultant blend, cooling the extrudate, and pelletizing.
  • a customary apparatus such as an extruder, a kneader, a Banbury mixer and a roll mill, extruding the resultant blend, cooling the extrudate, and pelletizing.
  • the melting and blending is generally conducted at about 170 to about 260 °C for about 15 to about 60 seconds.
  • the extrudate is cooled to about 10 to about 50 °C and then pelletized into pellets having a length of about 3 to about 5 mm and a diameter of about 2 to about 4 mm.
  • the polystyrene resin composition of the present invention has not only good appearance and excellent impact strength, but also improved stiffness. Therefore, the polystyrene resin composition of the present invention can advantageously be used, after molding, as parts or housings of household electric appliances, containers, daily necessaries, and the like. Particularly, the present polystyrene resin composition is advantageously used as a material for preparing a large molded article, such as a cabinet for a large-sized TV set or a frame for an air conditioner.
  • the flame-retardant polystyrene resin composition of the present invention has the above-mentioned excellent properties, molded articles of small thickness having sufficient stiffness and excellent flame retardance can be produced from the polystyrene resin composition. Therefore, the present composition is advantageous from the economic viewpoint as well.
  • the Izod impact strength at 23 °C for a notched sample was measured in accordance with ASTM D256.
  • the Vicat softening point was measured in accordance with ASTM D1525 (rate of temperature increase: 2 °C/min, load: 1 kg).
  • the melt flow rate was measured in accordance with ISO R1133 at 200 °C (load: 5 kg).
  • the surface of the molded article prepared by injection molding was observed with the naked eye.
  • a rubber-reinforced polystyrene resin, a fibrous potassium titanate and a higher fatty acid or its salt were blended by means of a blender in an weight amount ratio as shown in Table 1.
  • a rubber-reinforced polystyrene resin a high-impact polystyrene [Styron® (Dow Chemical Company, U.S.A.) H-8652, manufactured and sold by Asahi Kasei Kogyo Kabushiki Kaisha, Japan] (this polystyrene is hereinafter referred to as "HIPS-1”) was used as shown in Table 1.
  • stearic acid StAc
  • zinc stearate ZnSt
  • magnesium stearate MgSt
  • TISMO® D a product manufactured and sold by Otsuka Chemical Co., Ltd., Japan
  • Each of the resultant mixtures was melted and kneaded together, using a single-screw extruder having a screw diameter of 65 mm (Model HV-65-32 manufactured and sold by Tabata Industrial Machinery Co., Ltd., Japan), at 230 °C for about 15 seconds at a screw revolution rate of 120 rpm, extruded into 10 strands at an extrusion rate of 100 kg/hr, followed by cooling to 40 °C.
  • the cooled strands were pelletized to obtain pellets having a diameter of about 3 mm and a length of about 4 mm.
  • Pellets of polystyrene resin compositions were prepared in substantially the same manner as in Example 1 except that the raw materials shown in Table 2 were used.
  • Comparative Example 1 no fibrous potassium titanate was used.
  • Comparative Example 2 neither a higher fatty acid nor its salt was used.
  • Comparative Example 3 ethylenebisstearamide (EBS) was used instead of a higher fatty acid or its salt.
  • EBS ethylenebisstearamide
  • an ABS resin (Stylac® 101, manufactured and sold by Asahi Kasei Kogyo Kabushiki Kaisha, Japan) comprising a resin phase containing 31 % by weight of acrylonitrile (the ABS resin is hereinafter referred to as "ABS-1") was used instead of HIPS-1, and neither a higher fatty acid nor its salt was used.
  • an ABS resin (Stylac® 191, manufactured and sold by Asahi Kasei Kogyo Kabushiki Kaisha, Japan) comprising a resin phase containing 30 % by weight of acrylonitrile (hereinafter referred to as "ABS-2”) was used instead of HIPS-1.
  • a short glass fiber was used instead of a fibrous potassium titanate.
  • a high-impact polystyrene [Styron® (Dow Chemical Company, U.S.A.) H-8652, manufactured and sold by Asahi Kasei Kogyo K.K., Japan] 20 parts by weight of a fibrous potassium titanate having an average fiber diameter of 1.1 ⁇ m and an average fiber length of 30 ⁇ m (KISPACK, manufactured and sold by Kyushu Refractories Co., Ltd., Japan), 1.2 parts by weight of a carbon fiber (A-6000, manufactured and sold by Asahi Kasei Kogyo K.K., Japan), 18 parts by weight of decabromobiphenyl ether, 5 parts by weight of antimony trioxide, 4.5 parts by weight of a styrene-butadiene block copolymer (Tufprene, manufactured and sold by Asahi Kasei Kogyo K.K., Japan) and 0.4 part by weight of zinc stearate were subjected to
  • the cooled strands were pelletized to thereby obtain pellets of a flame retardant polystyrene resin composition.
  • the pellets had a diameter of about 2 to about 4 mm and a length of about 3 mm to about 5 mm. From the pellets, test pieces were obtained by injection molding.
  • Example 7 Substantially the same procedure as in Example 7 was repeated except that the amount of carbon fiber was changed to 2 parts by weight in Example 9 and 4.5 parts by weight in Example 10, to thereby obtain test pieces. The properties of the test pieces were determined and the results are shown in Table 3.
  • Example 7 Substantially the same procedure as in Example 7 was repeated except that the amount of fibrous potassium titanate was changed to 30 parts by weight and the amount of carbon fiber was also changed to 4 parts by weight, to thereby obtain a test piece. The properties of the test piece were determined and the results are shown in Table 3.
  • Example 7 Substantially the same procedure as in Example 7 was repeated except that the amount of fibrous potassium titanate was changed to 37 parts by weight and the amount of carbon fiber was also changed to 4 parts by weight, to thereby obtain a test piece. The properties of the test piece were determined and the results are shown in Table 3.
  • Example 8 Substantially the same procedure as in Example 8 was repeated except that a high-impact polystyrene [Styron® (Dow Chemical Company, U.S.A.) H-8117, manufactured and sold by Asahi Kasei Kogyo K.K., Japan] was used instead of Styron® H-8652, to thereby obtain test pieces. The properties of the test pieces were determined, and the results are shown in Table 3.
  • Example 12 Substantially the same procedure as in Example 12 was repeated except that the amount of fibrous potassium titanate was changed to 16 parts by weight, to thereby obtain test pieces. The properties of the test pieces were determined, and the results are shown in Table 3.
  • Example 8 Substantially the same procedure as in Example 8 was repeated except that a fibrous potassium titanate having an average fiber diameter of 0.2 ⁇ m and an average fiber length of 20 ⁇ m (TISMO® D, manufactured and sold by Otsuka Chemical Co., Ltd., Japan) was used instead of the fibrous potassium titanate having an average fiber diameter of 1.1 ⁇ m and an average fiber length of 30 ⁇ m, to thereby obtain test pieces.
  • the properties of the test pieces were determined and the results are shown in Table 3.
  • Example 7 Substantially the same procedure as in Example 7 was repeated except that the amount of fibrous potassium titanate was changed to 16 parts by weight and no carbon fiber was used, to thereby obtain test pieces. The properties of the test pieces were determined, and the results are shown in Table 4.
  • V-1 level In the test of flammability, some of test pieces burnt with glowing combustion for more than 30 seconds. These are classified as V-1 level and, therefore, a V-0 level could not be attained.
  • Example 7 Substantially the same procedure as in Example 7 was repeated except that the amount of fibrous potassium titanate was changed to 10 parts by weight, to thereby obtain test pieces. The properties of the test pieces were determined, and the results are shown in Table 4.
  • Example 8 Substantially the same procedure as in Example 8 was repeated except that the amount of fibrous potassium titanate was changed to 10 parts by weight, to thereby obtain test pieces. The properties of the test pieces were determined, and the results are shown in Table 4.
  • Example 7 Substantially the same procedure as in Example 7 was repeated except that the amount of carbon fiber was changed to 7 parts by weight, to thereby obtain test pieces. The properties of the test pieces were determined, and the results are shown in Table 4.
  • Example 7 Substantially the same procedure as in Example 7 was repeated except that the amount of carbon fiber was changed to 0.5 part by weight, to thereby obtain test pieces. The properties of the test pieces were determined, and the results are shown in Table 4.
  • the flammability level of the composition was V-1.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (9)

  1. Composition de résine de polystyrène de rigidité améliorée comprenant :
    (a) 100 parties en poids d'un homopolymère ou d'un copolymère renforcé par du caoutchouc d'un monomère aromatique monovinylique,
    (b) de 2 à 50 parties en poids de titanate de potassium fibreux, et
    (c) de 0.1 à 5 parties de poids d'un acide gras ayant de 12 à 22 atomes de carbone et/ou de son sel métallique.
  2. Composition de résine de polystyrène suivant la revendication, dans laquelle le titanate de potassium fibreux a une longueur moyenne de fibre de 10 à 60 µm et un diamètre moyen de fibre de 0.1 à 1.5 µm.
  3. Composition de résine de polystyrène suivant la revendication 2, dans laquelle le titanate de potassium fibreux a une longueur moyenne de fibre de 10 à 30 µm et un diamètre moyen de fibre de 0.1 à 0.8 µm.
  4. Composition de résine de polystyrène suivant l'une quelconque des revendications 1 à 3, dans laquelle la quantité du titanate de potassium fibreux est comprise entre 10 et 50 parties en poids.
  5. Composition de résine de polystyrène suivant l'une quelconque des revendications 1 et 2, dans laquelle la quantité du titanate de potassium fibreux est comprise entre 15 et 50 parties en poids.
  6. Composition de résine de polystyrène suivant la revendication 5, comprenant (d) de 4 à 35 parties en poids d'un agent retardant la propagation du feu et (e) de 1 à 5 parties en poids d'une fibre de carbone.
  7. Composition de résine de polystyrène suivant la revendication 6, dans laquelle le titanate de potassium fibreux a une longueur moyenne de fibre de 20 à 60 µm et un diamètre moyen de fibre de 0.5 à 1.5 µm.
  8. Composition de résine de polystyrène suivant l'une quelconque des revendications 1 à 7, dans laquelle l'acide gras est un acide gras saturé et le métal est choisi parmi les métaux des groupes II et III de la classification périodique des éléments.
  9. Procédé de préparation d'une composition de résine de polystyrène de rigidité améliorée, qui comprend les stades de :
    (1) mélange par fusion de
    (a) 100 parties en poids d'un homopolymère ou d'un copolymère renforcé au caoutchouc d'un monomère aromatique monovinylique,
    (b) de 2 à 50 parties en poids d'un titanate de potassium fibreux, et
    (c) de 0.1 à 5 parties en poids d'un acide gras ayant de 12 à 22 atomes de carbone et/ou de son sel métallique,
       entre 170 et 260°C,
    (2) d'extrusion du mélange obtenu, et
    (3) de refroidissement du produit extrudé entre 10 et 50°C.
EP89300102A 1988-07-28 1989-01-06 Composition de résine de polystyrène à rigidité modifiée Expired - Lifetime EP0352875B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP18676688 1988-07-28
JP186766/88 1988-07-28

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EP0352875A2 EP0352875A2 (fr) 1990-01-31
EP0352875A3 EP0352875A3 (en) 1990-10-24
EP0352875B1 true EP0352875B1 (fr) 1994-11-30

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JP (1) JPH02124957A (fr)
CN (1) CN1027543C (fr)
CA (1) CA1333311C (fr)
DE (1) DE68919569T2 (fr)
ES (1) ES2064430T3 (fr)
MY (1) MY104079A (fr)
SG (1) SG19695G (fr)

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JPH08183030A (ja) * 1994-12-28 1996-07-16 Daicel Chem Ind Ltd 長繊維強化耐衝撃性ポリスチレン樹脂構造体及びその成形品
CN100455896C (zh) * 2004-09-21 2009-01-28 乐金电子(天津)电器有限公司 咖啡机兼用微波炉的咖啡机外壳
CN102702666A (zh) * 2012-05-15 2012-10-03 昆山天卓贸易有限公司 钛酸钾晶须与abs改性的高抗冲复合材料及其制备方法
CN111019257B (zh) * 2019-12-13 2022-10-18 天津金发新材料有限公司 一种高韧性、耐热、耐磨的ps材料及其制备方法
CN111978652A (zh) * 2020-07-15 2020-11-24 日彩复合塑料(深圳)有限公司 一种打印机外壳料及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61152766A (ja) * 1984-12-27 1986-07-11 Fujikura Rubber Ltd 電磁波遮蔽用組成物
FR2575587B1 (fr) * 1984-12-27 1990-03-09 Otsuka Kagaku Kk Composition contenant un titanate de metal alcalin electriquement conducteur, et produits formes avec cette composition

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ES2064430T3 (es) 1995-02-01
EP0352875A2 (fr) 1990-01-31
CN1039822A (zh) 1990-02-21
JPH0561303B2 (fr) 1993-09-06
EP0352875A3 (en) 1990-10-24
CN1027543C (zh) 1995-02-01
DE68919569D1 (de) 1995-01-12
CA1333311C (fr) 1994-11-29
SG19695G (en) 1995-08-18
JPH02124957A (ja) 1990-05-14
MY104079A (en) 1993-11-30
DE68919569T2 (de) 1995-07-20

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